Photomasks are used in the art of photolithography for printing microelectronic circuits and other precision photofabricated parts, such as television shadow masks. In a photolithographic process a substrate is covered with a layer of photoresist in which a pattern is photographically developed by superimposing over the photoresist a photomask having patterned transparent and opaque areas, and then passing actinic radiation, especially ultraviolet light, through the transparent areas of the photomask. A pattern is then developed in the photoresist as a relief image by means of the differential solubilities of the exposed and unexposed portions. The resulting image may be either a negative or a positive image of the photomask, depending upon whether the photoresist is "negative-working" or "positive-working." Etching or other treatments may then be carried out on the underlying exposed portions of the substrate. A general discussion of the state of the art of photofabrication and the role played by photomasks may be found in Scientific American, September 1977, pages 111-128.
Since the preparation of a photomask can be laborious and costly, it is desirable for each photomask to be reused many times in the manufacture of photofabricated devices. Therefore, a photomask should be sufficiently durable to withstand extensive use, handling, and occasional cleaning without damage to the precision pattern it carries. It is also highly desirable to maximize the resolution of the pattern carried by a photomask so as to improve the accuracy of the image it imparts to the photofabricated devices being manufactured, which in turn permits further miniaturization of microcircuits and the like.
Photomasks in the prior art have typically consisted of sheets of glass carrying patterned coatings on their surfaces. Photographic emulsion, iron oxide, and chromium are the films most commonly used. While iron oxide and chromium are considerably more durable than photographic emulsion coatings, all three, by their very nature as coatings, are susceptible to scratching and other damage which shortens the useful life of the photomasks. Also, the etching required to produce a desired pattern in iron oxide or chromium films entails a loss of resolution due to the so-called "etch factor," which means that an etched groove grows wider as it grows deeper. This may be lessened by reducing the film thickness, but with a sacrifice in durability. Moreover, chromium films have the drawbacks of being opaque, which is a disadvantage when aligning the photomask with the substrate being processed, and of being reflective, which causes undesirable light scattering.
Photomasks of improved durability were proposed in U.S. Pat. No. 3,573,948 to M. S. Tarnopol and U.S. Pat. No. 3,732,792 M. S. Tarnopol et al., wherein instead of a coating on the surface of a glass sheet, the opaque areas of the photomask are produced by a stained pattern within the glass. While such stained glass photomasks represent a great improvement in durability, the degree of pattern resolution is less than what is desired for some applications. The limited resolution of the stained masks of the aforementioned patents arises from the necessity in one case to deeply etch the pattern through a stained layer of the glass, and in the other case to etch through a difficult-to-remove tin oxide coating, as well the tendency in both cases for a thermally migrated stain to spread laterally from the stained areas into the adjacent unstained areas during the staining process. A stained glass photomask is also shown in U.S. Pat. No. 3,561,963 to W. M. Kiba, where the desired pattern is etched into a copper film on the glass substrate and copper ions are then migrated into the glass by heating. In U.S. Pat. No. 3,933,609 to J. S. Bokov et al. the photomask is made by staining the entire surface of a sheet of glass and then selectively etching away portions of the stained layer.
Attempts to minimize lateral diffusion of the staining ions within the glass are disclosed in U.S. Pat. Nos. 2,927,042 to A. J. C. Hall et al. and 3,620,795 to W. M. Kiba. In those patents, a film of a stain-producing metal is deposited onto the glass and patterned portions of the film are removed by photoetching. Ions from the remaining patterned film are then migrated into the glass to produce stained areas by applying an electric field through the glass in the desired direction of ion migration while maintaining the glass at an elevated temperature. Since resolution is reduced each time the pattern is transferred to a different material, it would be highly desirable to reduce the number of steps required for such processes.
The use of electron bombardment to reduce stain-producing ions within glass to their elemental state was known in the prior art. For example, see Coloured Glasses by W. A. Weyl, Society of Glass Technology, Sheffield, England (1951), page 417. Some coloration affects of electron bombardment on some of the normal constituents of various glass compositions are disclosed in Reports of the Research Laboratory of Asahi Glass Company, Ltd., 25 1 (1975), pages 51 through 58. Also, the use of electron beams to produce coloration within films carried by glass substrates are disclosed in U.S. Pat. No. 3,720,515 to Stanley and U.S. Pat. No. 3,515,587 to Letter. An article by J. L. Lineweaver in J. Applied Physics, Vol. 34, p. 1786 (1963) discusses some coloration effects caused by sodium reduction in glass induced by electron bombardment. However, none of these references deal with injecting stain-producing ions into glass.